Cyanovinylene-triarylamines

ABSTRACT

Cyanovinylene-substituted triarylamine compounds produce fluorescent, light-fast greenish-yellow to yellow shades on polyester and cellulose acetate fibers.

United States Patent 91 Fisher et al. 1 Apr. 17, 1973 CYANOVKNYLENE-TRIARYL n i [56] References Cited [75] Inventors: John G. Fisher; Curtis E. Diebert, UNITED STATES PATENTS both of Kingsport, Tenn. 2,206,108 7/1940 Muller et a1 ..260/465 [73] Assignee: Eastman Kodak Company,

' Rochester Primary Examinerl ,ewis Gotts 2 e Jam 4 972 Assistant Examiner-Dolph H. Torrance Atl0rneyCecil D. Quillen, Jr. et a1. [21] Appl. No.: 215,439

ABS I RACT [52] US. Cl. ..260/465 D, 8/542, 8/179, cyanovinylene substimted tfiarylamine compounds 260/465 260/576 produce fluorescent, light-fast greenish-yellow to yel- [5 l Int. Cl.. ..C07C 121/70 low Shades on polyester and cellulose acetate fi [58] Field of Search "260/465 E, 465 D 7 Clains, No Drawings This invention concerns novel styryl compounds and, more particularly, it concerns styryl compounds which contain a triarylamine residue, are highly fluorescent and which are useful for dyeing polyester and cellulose acetate fibers.

Our novel compounds have the general formula NC R wherein R is cyano; lower alkoxycarbonyl; lower alkoxycarbonyl substituted with lower alkoxy, hydroxy, cyano,

halogen, succinimido, glutarimido or phthalimido;

aryloxycarbonyl; lower alkylsulfonyl; arylsulfonyl; or the group -CONR"R in which R is hydrogen, lower alkyl, aryl, or, when R is hydrogen, R also can be lower alkanoyl or lower alkoxycarbonyl, and R is hydrogen or lower alkyl; I

R is hydrogen, lower alkyl or lower alkoxy; and

R and R are the same or difi'erent and each is aryl;

in which each aryl group is phenyl or phenyl substituted with lower alkyl, lower alkoxy or halogen.

The novel compounds of the invention produce greenishyellow to yellow shades on polyester fibers when applied thereto according to conventional disperse dyeing techniques. Due to their fluorescence, our novel compounds produce unusually bright shades, especially when viewed under natural light. The styryl compounds also exhibit good fastness to light and dyeability properties.

The substituents encompassed by the generic terminology appearing in the above definitions of R through R are well known in the art and can be derived from known compounds according to published procedures. As used herein to describe an alkyl moiety, lower designates a carbon content of 1 to about 4 carbon atoms. Chlorine and bromine are preferred halogen atoms which can be present on our novel compounds.

The compounds of the invention which, because of their excellent costzperformance ratio, are especially valuable for dyeing polyester fibers are those in which R is cyano or lower alkoxycarbonyl, R is hydrogen or methyl and R and R" each is phenyl or tolyl.

The novel compounds of the invention are prepared by the condensation of a triarylamine aldehyde and an active methylene compound. This v condensation is generally conducted under basic conditions in an organic solvent at a temperature of 60 to 100C. For example, the reaction can be conveniently conducted in benzene at reflux with piperidine as the basic catalyst. The styryl compounds can be isolated by cooling the reaction mixture, whereupon the product crystallizes from solution.

The triarylamine aldehyde intermediates are prepared by formylation of the corresponding triarylamines with a Vilsmeier-type formylating agent.

The formylation generally proceeds smoothly and in high yield. Depending upon the position, of the substituent, if any, represented by R and any substituents present on the phenyl nuclei of aryl groups R and R,

the formylation of the triarylamine precursors can result in the formation of multiple formylation products which, when condensed with the active methylene compound, yield a mixture of methine compounds. Such a mixture of methine compounds, consisting of at least two compounds conforming to Formula (I), can be used to produce bright shades on polyester fibers as described hereinabove. The triarylamines can be prepared by the well-known Ullman reaction. For example, triphenylamine is prepared by the treatment of diphenyla mine with iodobenzene in the presence of copper or copper-bronze and potassium carbonate. The active methylene compounds having the formula R -Ci-l --CN are known compounds and/or can be prepared by known means.

The following examples further illustrate the preparation and use of our novel compounds.

EXAMPLE 1 p-Diphenylarninobenzaldehyde (1.37 g., 0.005 mole), malononitrile (0.36 g., 0.0055 mole), ethanol (20 ml.), and piperidine (1 drop) are combined and heated at reflux for 1 hr. The mixture is then chilled in an ice bath and filtered. An orange, crystalline solid (1.30 g.) is obtained. The product, p-diphenylaminobenzylidenemalononitrile, is recrystallized from ethyl acetate; m.p. 137l 38.5C.; visible A max 431 nm. (acetone). Anal. Calcd. for C I-1, 1%: C, 82.22; H, 4.71; N, 13.07 Found: C, 82.17; H, 4.76; N, 13.18 The brilliant, fluorescent, yellow product obtained displays excellent dyeing and fastness properties on cellulose ester and polyester fibers.

EXAMPLE 2 p-Diphenylaminobenzaldehyde (54.7 g., 0.2 mole), ethyl cyanoacetate (24.9 g., 0.22 mole), absolute ethanol (350 ml.), and piperidine (1 ml.) are combined and heated at reflux for 3 hr. The mixture is chilled, filtered, and the solid yellow product, ethyl p-diphenylamine-a-cyanocinnamate (67.4 g.), is recrystallized from ethanol-ethyl acetate; m.p. l18121C.; visible A max 420 nm. (acetone). Anal. Calcd. for C H N O C, 78.24; H, 5.47; N, 7.61

Found: C, 78.36; H, 5.56; N, 7.59 The brilliant greenish-yellow, fluorescent compound obtained displays excellent dyeing and fastness properties on cellulose ester and polyester fibers.

EXAMPLE 3 The procedure of Example 1 is repeated except that malononitrile and p-diphenylarninoo-methoxybenzaldehyde are employed as starting materials. The yellow solid obtained is recrystallized from ethyl acetate; m.p. l79-181C., visible A max 427 nm. (acetone). The brilliant yellow, fluorescent compound, p(n-phenyl-oanisidino)benzylidenemalononitrile, obtained displays excellent dyeing and light-fasmess properties on cellulose ester and polyester fibers.

The styryl compounds set forth in the examples of the following Table conform to Formula (I) and are prepared by the procedures described hereinabove. The color given for each of the compounds of the following examples refers to the shade it produces on polyester fibers. The position of substituent R relates to the triarylamine nitrogen atom.

"Cally,

The polyester and cellulose acetate fibers which can be dyed with our novel compounds and the dyeing NC R wherein R is cyano; lower alkoxycarbonyl; lower alkoxycarbonyl substituted with lower aikoxy, hydroxy, cyano, halogen, succinirnido, glutan'mido or phthalimido; ary loxycarbonyl; lower alkylsulfonyl; arylsulfonyl; or

A I? the g toup coNR R in which R is hydrogen, lower alkyl, aryl or, when R is hydrogen, R also can be lower alkanoyl or lower alkoxycarbonyl, and R is hydrogen 7 or lower alkyl;

R and R each is pheng l or tolyl. 3. A compound accor g to claim 1 having the for- 4. A compound according to claim 1 having the formula NC Q

:011 N I clmooc Q 5. A compound according to claim 1 having the formula NC I Q" C=CH N 6. A compound according to claim 1 having the formula Q 40 /C'=OH N I 7. A compound according to claim 1 having the formula i NC Q C=CII -N a: k a: 

2. A compound according to claim 1 wherein R1 is cyano or lower alkoxycarbonyl; R2 is hydrogen or methyl; and R3 and R4 each is phenyl or tolyl.
 3. A compound according to claim 1 having the formula
 4. A compound according to claim 1 having the formula
 5. A compound according to claim 1 having the formula
 6. A compound according to claim 1 having the formula
 7. A compound according to claim 1 having the formula 